Manufacture of ketones and aldehydes



Patented Au 1 9, 1 1

UNITED STATES PATENT orrica scram MANUFACTURE OF KETONES AND ALDEH'IDES Vladimir-KI land mamas. Schaad, 'fihloagmmmi'norstoUnivu-nl Oill'rodnots Co pany. were N 1mm. mantis... 15, ms,

'' Serial No. 185.155

8 China. (Cl. 280-597) methyl acetylene, ketones are formed as shown by the following equation indicating the formation of acetone from methyl acetylene.

These reactions are ordinarily brought about using such catalysts as sulfuric-acid or solutions of mercuric salts.

The value of aldehydes and ketones as commercial products does not need any extensive recounting since these compounds have not only value in themselves as solvents and reagents, but also form the basis for the manufacture of a large number of derivatives which have special uses in the arts and it is with improvements in a type of reaction which produces good yields oi these compounds that the present invention .is concerned.

In one specific embodiment the present invention comprises the manufacture of acetaldehyde and various ketones by the interaction of acetylene and its various alkyl derivatives, respecmixes. the former at ordinary temperatures and.

the latter, at temperatures of approximately 160-180 C. to insure proper fluidity and inti-.

mate mixing. Catalysts of the foregoing character are apparently composed of certain proportions of silico-phosphoric acid complexes. unacted upon carrier, and a percentage of a free phosphoric acid which appears from analysis to be most closely related in composition to the pyro acid having theformula H4Pz01. In the present instance catalysts of this type may act by virtue In. case the hydrogen atoms in theacetylene are substituted by an alkyl group, as in the case of of their ability to 'form addition products with the acetylene or acetylene derivatives and also by virtue of their ease of hydration and deny-.-

dration, assuming the intermediate compound theory of catalysis as a possible explanation.

In operating the process the catalyst is preferably placed in a vertical cylindrical treating chamber having a perforated false bottom or a screen forsupporting the catalyst bed and a proportioned mixture of hydrocarbon and steam is passed downwardly through the catalyst bed at substantially atmospheric pressure and an optimum rate and temperature both of which latter conditions will vary somewhat with the activity of the catalyst and with the particular acetylene undergoing treatment. Unchanged hydrotively, with steam at temperatures in the approximate range of 150-300 C. in the presence of solid phosphoric acid catalysts.

The type of catalysts which have been found specially effective in promoting the present type of reaction are produced by the general'steps of mixing phosphoric acids (usually in major proportion) with relatively inert spacing materials such as; for example, kieselguhr or certain clays until a paste is obtained, calcining the pasty ma- 1 terial at a temperature of the order of (SOD-400 C. toproduce a solid cake, grinding the cake to produce granules of approximately 4-20 mesh and finally subjecting the granules to contact with steam at temperatures of the order of 250-260 C; and at substantially atmospheric pressure to produce an acid of the composition corresponding to maximum catalytic activity. The foregoing procedure may be varied by forming particles of the original paste by extrusion or pelleting methods and then following by the steps of calcining and rehydrating. Either ortho or pyro phosphoric acid may be used in the primary carbons may be separated from the reaction products and steam and recirculated for further conversion reactions so that a high conversion is made possible.

In the production or acetaldehyde from acetylene and steam, approximately equivalent molecular quantities of reactants are employed, and temperatures of about 300 C. Under these conditions approximately of the acetylene is reacted in a single pass and acetaldehyde is produced in an-amount approximately equivalent to the theoretical yield calculated from the quantity of water which was consumed in the reaction. There is concurrently some formation of higher boiling oily material which may correspond to high molecular weight condensation products of either acetylene or acetaldehyde, and in general the formation of such products is avoided by maintaining a relatively low temperature and low rate of reaction particularly in thecase of fresh and active catalysts. As the catalyst activitydecreases due to the gradual building up of carbonaceous deposits on its surface, the temperature is preferably increased to compensate for its loss in activity.

Formation of ketones from the alkyl derivatives of acetylene .is usually accomplished at somewhat lower temperatures than those required for the production of acetaldehyde from acetylene, these temperatures being principally comprised within the range of to 300 C. In all instances unconverted hydrocarbon may be recycled to increase the ultimate yield.

The regenerationoi spent catalyst is brought about by the general steps or oxidizing oi! carbg'naceou's materials by passing oxidinng gas ratio oiwater to hydrocarbon of 2.5:1 down through a 8-10 mesh solid phosphoric acid cata-' mixtures through thecatalyst bed. The best method which prevents undue rise in temperature due to the decomposition reactions and hcnce preserves the structure and other desirable properties oi the catalysts consists in utilizing primarily combustion gases of relatively low oxygen content and gradually increasing the oxygen content by the addition of air until finally air alone is used. Usually best results in reactivation are obtained when gas mixtures containing less than by volume 0! water vapor are employed are not exceeded in the burning period. After the removal oi carbonaceous deposits the catalyst andwhen temperatures of approximately 950 F.

lyst maintained at a temperatureoi 200 C. The

yield of methyl. ethyl ketone was 58% baseduponthe hydrocarbon charged alongwith the produce tlon 01'. approximately or high boiling liquid is preferably further subjected to theaction 01' Y superheatedsteam at atmospheric pressure and temperatures oi. from 250-280 C. to rehydrate the phosphoricacid, apart 0!, which apparently The following examples are. given tov indicate the results normally obtainable in the practical application oi the present process although not with the intention of unduly circumscribing its proper scope.

Example I The following tabulation of data includes the in acetylene and steam were passed downwardly through granular solid phosphoric acid catalyst As will be seen from the above table the yield 0i acetaldehyde under the best conditions 0! op- Example]! l in this case substantially pure ethyl acetylene is converted to the inactive meta acid during the burning P riod. 1

4 'signiilcantflgures obtained in three runs whereproducts principally oi a hydrocarbon character. 7 The nature 01 the-present invention and its novel and commercial utility are obvious item the preceding descriptive and numerical sections, 9.1-

though neither is intended to unduly limit its I We claim as our invention: l. A process tor producing acetaldehyde which comprises reacting acetylene with steam in the presence of a calcined mixture of a phosphoric acid and a siliceous material capable of forming a silico-phosphoric acid complex.

2. A process for producing acetaldehyde which I comprises reacting acetylene with steam in the presence of a calcined mixture of a phosphoric acid and a siliceous material capable of forming a lsllico-phosphoric acid complex at a temper ature in the approximate range 0! ISO-300 C. 3. A process for producing ketcnes which com prises reacting an alkyl acetylene with steam in the presence of a calcined mixture of a phosphoric acid and a siliceous material capable of forming a since-phosphoric acid complex.

under the condltioiis indicated:

. i I I Run number Fresh ,7 After reactivacatalyst tlon I I V I Duration of run-..". -....'....hours 21 23 22 Tern rature': .J 300 x 300 300 gatal y s t, Mfl'extruded "grams" 100 98 98 o Y wau lz c cvapgratfd gin c3231..." 220 227 228 a a conhit a. s1 10. so 5.10 i h we grams 220 227 220 Acct lonedo 289 338 167 Total charge ..do 509 565 308 note: r Exit ace lone .-cu. it. 6. 48 6. so 8. 94 Exit aoaglene grams. 162. 00 201. 00 no. 50 Acetaldehyde --.do 71. 60 74. so 48.11 Water lay dc 187. 90 l90.00 203. Oil layer ..do.... 88.48 21.2) 4.40 Recove percent by weight oi charge" 94. so 89. 80 I 05.0 Abso t on of acetylene ..percent.. 44 40 ill Acety ne consumed ..grams.. 127 137 50. 5 Water consumed .grams 33 37 22. 6 4 Theoretical yield of acetaldehyde calculated irom water consumed...grams. 8) 90 65 Actual yield, percent of theoretical 89. 5 82. 8 87. 6

4. A process for producing ketones which comprises reacting an alkyl acetylene with steam in the presence 01' a calcined mixture of a phosphoric acid and a siliceous materialcapable' oiiorming a silica-phosphoric acid complex at a temperature in the approximate range of loll-300 C.

5. A process for producing acetone which com prises reacting methyl acetylene with steam in the presence 01' a calcined mixture of a phosphoric acid and a siliceous material capable oi forming a sillco-phosphoric acid complcx.- 1 6. A process for producing acetone which comprises reacting methyl acetylene with steam in the presence of a calcined mixture of a phosphoric acid and asiliceous materialcapable oi forming a since-phosphoric acid-complex at a temperature in the approximate range of rec-300 C. f

'l. A process forthe manufacture of organic compounds containing a carbonyl radical from acetylene hydrocarbons selected from the group consisting oi acetylene and its alkyl derivatives. which comprises reacting the acetylene hydrocarbon with steam in the presence of a calcined mixture oi a phosphoric acid. and a siliceous mate-. rial capable of forming a silico-phosphoric acid complex. I

8. A process for the manufacture of organic compounds containing a carbonyl radical from acetylene hydrocarbons selected from the group consisting of acetylene and its alkyl derivatives, which comprises contacting the acetylene hydrocarbon, in admixture with steam, with a calcined mixture of a phosphoric acid and a siliceous material capable of forming a silica-phosphoric acid complex in the approximate range of loo-soc c. v v

VLADIMIR. N. IPATIEFF. RAYMOND a. serum. 

